Generation Mechanism of Persistent Free Radicals in Lignocellulose-Derived Biochar: Roles of Reducible Carbonyls.

Persistent free radicals (PFRs) in biochar can influence biochar reactivity, promoting organic contaminant degradation or even causing certain toxic impacts. However, the PFR generation mechanism is not still well understood. An investigation of the relationship between PFR formation and the chemical structure of biochar is essential for understanding the PFR formation mechanism. Our in situ measurement results showed that PFR intensities increased from 0-509.5 to 146-5678 a.u. after being pyrolyzed at 300 °C for 60 min. The significant positive correlation between PFR intensities and the peak areas of C═O and aromatic C═C groups indicated that the generation of PFRs was highly dependent on the C═O and aromatic C═C structures. The reduction of biochars by KBH4 resulted in a 32.2 ± 2.49% decrease in the C═O content and a relative increase in the C-O content, while other physicochemical properties did not change. Thus, the observed 49.3% decrease in PFR signals after this reduction suggested that the reducible C═O groups, possibly in aldehydes, aromatic ketones, and quinones, were closely associated with PFRs in biochars. This study provides an in situ insight into the PFR generation mechanism and guides the corresponding biochar design and property manipulation.